Soil conditioning agglomerates containing calcium

ABSTRACT

Mechanically strong, water-disintegrable agglomerates made from a particulate calcium source, a water-soluble binder and optionally containing a primary plant nutrient source and/or micronutrient source and a process for forming such agglomerates are disclosed. The agglomerates may be used as a soil liming agent and for introducing nutrient values into cultivated soil. Also disclosed is a method for introducing nutrient values into cultivated soil so as to inhibit leaching of the nutrient values from the soil and improve utilization of the nutrient values by plants grown in the soil.

This application is a continuation of U.S. Ser. No. 09/300,024, filed Apr. 27, 1999, abandoned, which claims the benefit of U.S. provisional application Ser. No. 60/083,232, filed Apr. 27, 1998, the disclosure of which is expressly incorporated herein by reference, and which also is a continuation-in-part of U.S. Ser. No. 09/067,064, filed Apr. 27, 1998, now U.S. Pat. No. 5,997,599, which is a continuation of U.S. Ser. No. 08/672,226, filed Jul. 5, 1996, now U.S. Pat. No. 5,743,934, which is a continuation-in-part of U.S. Ser. No. 08/398,657, filed Mar. 3, 1995, abandoned. This application is also a continuation-in-part of U.S. Ser. No. 09/067,283, filed Apr. 27, 1998, now U.S. Pat. No. 6,287,356, which is a continuation-in-part of U.S. Ser. No. 08/672,226, filed Jul. 5, 1996 now U.S. Pat. No. 5,743,934, which is a continuation-in-part of U.S. Ser. No. 08/398,657, filed Mar. 3, 1995, abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to mechanically strong, water-disintegrable agglomerates containing various particulate calcium sources for use as a soil conditioner to neutralize soil acidity and provide a source of nutrient values. The present invention also relates to processes for forming such agglomerates as well as to methods of introducing nutrient values into cultivated soil so as to inhibit leaching of the nutrient values and improve utilization of the nutrient values by plants grown in the soil.

Soil conditioners or liming agents are widely used in agriculture, lawn care and gardening to reduce soil acidity and promote plant health. A variety of calcium-containing materials, in particulate or granulated form, are used as soil liming agents. Conventional liming agents include: limestone, dolomitic limestone, lime, slaked or hydrated lime, and gypsum.

Many industrial processes produce waste solids containing calcium. For example, the manufacture of cement and lime is accompanied by the generation of large quantities of dust collected from the hot gaseous effluents vented from the kiln. Similar calcium-containing dusts are recovered from the stack gases and ash residues produced during the burning of manure fuels (i.e., manure ash). These particulate wastes share two properties that make them potentially useful for application to cultivated soils: (1) significant acid neutralization capacity; and (2) high concentrations of calcium and other important soil nutrients such as potassium and sulfur. It has been suggested to use calcium-containing waste solids such as cement kiln dust to lime cultivated soil (See T. A. Davis, et al., “Disposal and Utilization of Waste Kiln Dust From Cement Industry”, EPA Report No. 670/2-75-043 (May 1975)) as a way of reclaiming these sizeable waste streams. However, expanded agricultural-utilization of these waste products has been hindered by problems associated with storage, handling and application of these finely divided materials to soils. Raw cement kiln dust exiting the kiln, for example, is extremely fine, typically consisting of particles having an average particle size much less than 100 μm, with a large portion of particles often having a particle size of 10 μm or less. As a result, the dust is easily carried away by the wind and is difficult to bulk-blend with other materials in preparing various fertilizer formulations. Furthermore, modern fertilizer application equipment for broadcast or row placement of solid fertilizers, is designed for handling free-flowing, granular or pelletized materials having an appreciable mean diameter, not dust. Consequently, numerous problems are encountered when such equipment is employed for field application of finely-divided dust.

It would be highly beneficial to develop a process for granulating or agglomerating cement kiln dust and similar calcium-containing waste materials capable of consistently producing a mechanically strong soil conditioning agglomerate that readily disintegrates when contacted with water. In addition, it would be advantageous to improve the efficacy of agricultural liming agents generally and provide agglomerate compositions for introducing nutrient values into cultivated soil so as to inhibit leaching of the nutrient values and improve utilization of the nutrient values by plants grown in the soil.

SUMMARY OF THE INVENTION

Among the objects of the present invention, therefore, are the provision of a process for forming an agglomerate comprising calcium-containing waste materials such as cement kiln dust for use as a soil conditioning agent; the provision of such a process capable of producing an agglomerate having sufficient mechanical strength to withstand the rigors of handling, transport and application without excessive dusting; the provision of such a process which produces an agglomerate which disintegrates readily into particles having substantially the same size as the raw materials used to form the agglomerate once the agglomerate is incorporated into soil and exposed to water so that the various beneficial components of the agglomerate may be rapidly utilized by plants grown in the soil; and the provision of soil conditioning agents and agglomerate compositions made from calcium-containing waste materials as well as from conventional agricultural liming materials combined with plant nutrient values exhibiting improved efficacy.

Briefly, therefore, the present invention is directed to a process for forming an agglomerate for use as a soil conditioning agent. The process comprises preparing a preagglomerate containing a water-soluble binder and a particulate calcium source. The particulate calcium source has a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and less than about 25% by weight of the particulate calcium source is −100 +200 mesh Tyler Standard Sieve Series. The preagglomerate-is pelletized to form the agglomerate. In accordance with another embodiment, the preagglomerate additionally contains a primary plant nutrient source and the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series.

The present invention is further directed to an agglomerate for use as a soil conditioner and to provide a source of nutrient values. The agglomerate is formed by pelletizing a preagglomerate containing a particulate calcium source, a primary plant nutrient source and a water-soluble binder. The proportions of the particulate calcium source and the primary plant nutrient source in the preagglomerate are sufficient such that the agglomerate comprises about 15% to about 60% by weight of the particulate calcium source and about 30% to about 80% by weight of the primary plant nutrient source. The particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series. The agglomerate having a size ranging from −7 to +8 Tyler Standard Sieve Series exhibits an average green crush strength of at least about 2 pounds.

The present invention is also directed to a method for introducing nutrient values into cultivated soil so as to inhibit leaching of the nutrient values from the soil and improve utilization of the nutrient values by plants grown in the soil. The method comprises applying to the soil an agglomerate comprising about 15% to about 60% by weight of a particulate calcium source, about 30% to about 80% by weight of a primary plant nutrient source and a water-soluble binder. The particulate calcium source exhibits a calcium carbonate equivalent value in excess of about 85% and has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series. The agglomerate readily dissolves upon exposure to water to disintegrate into particles of the particulate calcium source and primary plant nutrient source.

Other objects and features of this invention will be in part apparent and in part pointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a flow diagram of one embodiment of the process of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention, mechanically-strong, water-disintegrable agglomerates produced from various particulate calcium sources including calcium-containing waste materials as well as conventional soil liming agents are provided. The agglomerates are useful as soil conditioners to neutralize soil acidity and provide a source of nutrient values. Processes for forming the agglomerates are also provided. The agglomerate compositions in accordance with the present invention are useful in introducing nutrient values into cultivated soil in a manner such that leaching of the nutrient values is inhibited and utilization of the nutrient values by plants grown in the soil is improved.

As used herein, agglomerate means pellets and irregularly-shaped particles formed by the consolidation of smaller particles. All mesh sizes herein are in reference to the Tyler Standard Sieve Series.

The agglomerates of the present invention are made by pelletizing a preagglomerate mixture prepared by combining a water-soluble binder with a particulate calcium source as described in detail below.

The particulate calcium source may comprise cement kiln dust, lime kiln dust, manure ash or other calcium-containing secondary plant nutrient sources including conventional liming agents such as limestone, dolomitic limestone, lime, hydrated lime and gypsum. The particulate calcium source may consist essentially of any one of the aforementioned calcium-containing materials as well as mixtures thereof. The gypsum may be derived from natural sources as well as from byproducts of chemical operations such as the wet solids and slurries produced in lime scrubbing stack gases to remove sulfur dioxide. In general, the agglomerates contain at least about 15% by weight of the particulate calcium source. If cement kiln dust, lime kiln dust, manure ash or other calcium-containing waste materials are combined with another calcium-containing secondary plant nutrient source, it is preferred that the other calcium sources constitute no more than about 80% by weight of the particulate calcium source, more preferably from about 30% to about 70% by weight of the particulate calcium source. In order to achieve the mechanical strength and disintegration characteristics desired in the agglomerate, the amount of water-soluble binder present in the preagglomerate is generally at least about 1% by weight (dry basis). Use of larger quantities of binder generally yields higher strength agglomerates which may be desirable in some applications. Preferably, the amount of binder present in the preagglomerate is at least about 2%, more preferably, at least about 4% by weight (dry basis). Preferably, the amount of binder present in the preagglomerate is between about 4% and about 25% by weight (dry basis).

Suitable water-soluble binders for use in the present invention include lignosulfonates, lignosulfonate salts (e.g., calcium lignosulfonate, ammonium lignosulfonate), water-soluble fertilizer materials (e.g., potash, ammonium nitrate, urea, diammonium phosphate), synthetic or naturally occurring polymers (e.g., polyvinyl alcohol, polyacrylic acid salts, amylose, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose, corn starch and wheat starch) and sugar-based binders such as molasses and those sold by RDE, Inc., Crystal Lake, Ill., 60014 under the “BREWEX” and “MOLTECH” trademarks, as well as mixtures of these various materials. Among the preferred binders for use in the present invention are the liquid blends of granulating agents and surfactants sold by Arr-Maz Products, Winter Haven, Fla. 33880, under the product designations KGA-300 and KGA-250. An especially preferred binder is the calcium salt of lignosulfonate such as that sold by LignoTech USA, Greenwich, Conn. 06830, under the trademark “NORLIG A”.

In addition to the particulate calcium source and water-soluble binder, the agglomerates may contain appreciable amounts of various particulate additives. For example, the agglomerates may comprise a primary plant nutrient source (i.e., a source of nitrogen, phosphorous and/or potassium), a secondary plant nutrient source (i.e., a source of magnesium, sulfur, and/or calcium), and/or a micronutrient source (e.g., a source of iron, copper, boron, selenium, chromium, vanadium, manganese, zinc and/or molybdenum). Upon disintegration of the agglomerate, these additives deliver their benefit to the soil along with the particulate calcium source. Although the particulate calcium source may contain appreciable quantities of certain primary plant nutrients, secondary plant nutrients and/or micronutrients, it should be understood that primary plant nutrient source, secondary plant nutrient source and micronutrient source as used herein means an additive apart from the particulate calcium source intended to increase the concentration of a desired nutrient or micronutrient in the agglomerate product.

For some applications, the agglomerate may contain only a particulate calcium source and a water-soluble binder, whereas in other applications the particulate calcium source will account for from about 15% to about 50% of the weight of the agglomerate. In those applications where it is desired to introduce nutrient values into cultivated soil, it is desirable to combine the particulate calcium source with appreciable quantities of a primary plant nutrient source of the type typically used in nitrogen-phosphorus-potassium (N-P-K) fertilizer formulations in the agglomerate. For example, the agglomerate may contain conventional sources of nitrogen, phosphorous and potassium such as ammonium nitrate, ammonium sulfate, alkali metal nitrates, urea, rock phosphate, ammonium phosphate (e.g., (NH₄)₂HPO₄, NH₄H₂PO₄.H₃PO₄ and NH₄H₂PO₄) bone meal slag, aluminum phosphate, superphosphate, potash, and potassium salts (e.g., chlorides, sulfates and nitrates) and mixtures thereof. The agglomerate may also contain organic fertilizer ingredients such as manure and residues from sewage treatment plants. For such applications, it is preferred that the agglomerate contain from about 5% to about 40% available nitrogen, more preferably from about 8% to about 15% available nitrogen, about 10% to about 50% available phosphoric acid, and/or about 10% to about 50% available potash. If urea, potash or other N-P-K fertilizer ingredient is used as a binder, this also has the further beneficial effect of increasing the primary plant nutrient content of the agglomerate. Furthermore, if desired, the agglomerates may additionally include a micronutrient source. Conventional sources of micronutrients may be used. For example, boron may be added in the form of disodium octaborate tetrahydrate.

A preferred agglomerate for use in introducing N-P-K nutrient values into cultivated soil contains about 30% to about 80% by weight of a primary plant nutrient source and at about 15% to about 60% by weight of the particulate calcium source, based on the weight of the agglomerate. A preferred agglomerate for use in introducing nitrogen into cultivated soils contains about 30% to about 80% by weight, more preferably about 55% to about 60% by weight, urea or other source of available nitrogen (e.g., ammonium nitrate) and at least about 15% to about 60% by weight, more preferably about 35% to about 45% by weight of the particulate calcium source, based upon the weight of the agglomerate. In accordance with another preferred embodiment, an agglomerate for use in introducing potassium into cultivated soil contains about 30% to about 80% by weight, more preferably about 45% to about 55% by weight, potassium chloride, potash or other source of potassium and at least about 15% to about 60t by weight, more preferably about 45% to about 50% by weight of a calcium source, based upon the weight of the agglomerate. In these formulations, the N-P-K fertilizer ingredients function as a binder for the agglomerate as well as a nutrient source. To improve the mechanical strength, these preferred agglomerates may further comprise an additional binder such as one of the lignosulfonate binders disclosed herein.

Depending on the selection of materials used in the particulate calcium source, the particulate calcium source may contain appreciable quantities of CaO and may further contain other calcium-containing compounds having the potential to react with water and form a solid hydrate, such as calcium sulfate (CaSO₄) and calcium sulfite (CaSO₃), which may be present in anhydrous or partially-hydrated forms. Other compounds such as MgO and Na₂SO₄ will also hydrate, but are typically present in smaller proportions.

Cement kiln dust, lime kiln dust and manure ash, for example, may contribute significantly to the concentration of CaO and other calcium-containing compounds having the potential to be hydrated present in the particulate calcium source. The composition of cement kiln dust can vary significantly with the composition of the raw materials fed to the kiln, the kiln system, the fuel used to fire the kiln as well as the conditions encountered by the dust particles in the kiln and in the dust collection apparatus. Generally, cement kiln dust is comprised of varying amounts of elements such as Ca, Mg, Si, Al and Fe, trace amounts of heavy metals and a distribution of alkalies such as K, Na and Li. Most of these elements are present as carbonates, sulfates, halides, hydroxides, oxides or silicates. Since the kiln dust has undergone some degree of calcination, the CaCO₃ content in the dust is depleted relative to the kiln feed and a significant portion of the calcium is instead present as CaO. Due to its composition which includes CaO, raw cement kiln dust exiting the kiln is highly-reactive toward water and has the potential to hydrate and harden if exposed to sufficient moisture.

A representative cement kiln dust composition is set forth in Table 1 below. However, it should be understood that Table 1 is intended as merely exemplary and cement kiln dust need not include all of these constituents in the concentrations listed below nor are other possible constituents excluded.

TABLE 1 Constituent % By Weight CaCO₃ 30-60 CaO  5-40 SiO₂ 10-20 Al₂O₃ 2-6 Fe₂O₃ 1-4 MgO 1-4 K₂SO₄ 3-9 CaSO₄ 2-8 Na₂SO₄ 1-3 KCl 1-3 KF 0.1-1   Heavy Metals trace

Like cement kiln dust, lime kiln dust and manure ash are finely divided and contain high concentrations of calcium compounds, including CaO, and are similarly reactive toward water and have the potential to hydrate and harden when exposed to moisture. Although similar in composition to cement kiln dust, an even larger proportion of calcium present in lime kiln dust is in the form of CaO. Lime kiln dust may contain 50% by weight or more CaO. Of course, the use of lime in the particulate calcium source will also increase the CaO content.

When cement kiln dust, lime kiln dust, manure ash and lime are contacted with water, CaO and other calcium-containing compounds present having hydration potential react with the water and are hydrated. In the case of CaO, the reaction product is Ca(OH)₂, whereas calcium sulfate reacts with water to form gypsum. The reaction of these components with water is accompanied by a volumetric expansion or enlargement as they are converted to their hydrate form. The hydration of CaO to Ca(OH)₂ lime is believed to be accompanied by a particularly significant volumetric expansion. That is, it is believed that the potential of the particulate calcium source used in the practice of the present invention, and ultimately that of the preagglomerate mixture, to hydrate and expand is predominantly attributable to the presence of CaO.

In the practice of the present invention, the preagglomerate mixture comprising the particulate calcium source and the other various components of the product is agglomerated using conventional tumble or growth agglomeration methods which include contacting the mixture with water in a suitable agglomeration device. The volumetric expansion which accompanies the hydration of CaO and other calcium-containing compounds having the potential to be hydrated present in the preagglomerate may tend to reduce the mechanical strength of the agglomerates if the concentration of these compounds in the preagglomerate is excessive. In general, it has been discovered that if the combined concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate exceeds about 10% by weight (dry basis), the subsequent volumetric expansion of these components can significantly reduce the mechanical strength of the agglomerates. Therefore, the combined concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture is preferably no greater than about 10%, more preferably no greater than about 7%, still more preferably no greater than about 5% and optimally no greater than about 3% by weight on a dry basis. Controlling the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture in this fashion advantageously minimizes the extent to which the resulting agglomerate will swell upon hydration so that an agglomerate exhibiting sufficient mechanical strength may be produced.

The concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture may be controlled simply by limiting the amount of the sources of these compounds introduced into the preagglomerate. For example, if cement kiln dust containing about 30% by weight CaO is the only source of CaO and other calcium-containing compounds having the potential to be hydrated in the particulate calcium source, the amount of cement kiln dust introduced into the preagglomerate preferably does not exceed about 33% by weight, more preferably does not exceed about 23% by weight, still more preferably does not exceed about 17% by weight and optimally does not exceed about 10% by weight of the preagglomerate mixture. In addition, limiting the proportion of cement kiln dust, lime kiln dust and/or manure ash in the preagglomerate may permit the use of such materials containing relatively high concentrations of heavy metals (e.g., mercury, lead, arsenic etc.) or other potentially harmful components. That is, the balance of ingredients in the preagglomerate serve as a buffer to reduce the concentration of these components in the agglomerates so as to produce a suitable liming product that conforms with environmental guidelines.

Alternatively, the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture is controlled by prehydrating all or a portion of the components of the particulate calcium source containing such compounds. For example, upon contacting cement kiln dust with water, CaO, CaSO₄, CaSO₃ and other components of the dust having hydration potential react with the water and are hydrated, thereby reducing the hydration potential of the cement kiln dust and ultimately of the preagglomerate. Preferably, the material to be prehydrated is combined with an amount of water less than the stoichiometric amount necessary to totally hydrate the components of the material in order to ease subsequent handling of the hydrated material in the agglomeration process. As the amount of water combined with the material to be prehydrated approaches or exceeds the stoichiometric amount needed to totally hydrate the material, it becomes increasingly difficult to form acceptable agglomerates because the hydrated material begins to cement together into progressively larger particles which ultimately produce agglomerates that do not readily disintegrate when exposed to water. By combining the material to be prehydrated with an amount of water less than the stoichiometric amount necessary to totally hydrate the material, the partially-hydrated material remains substantially dry and free-flowing and can be easily combined with the other components of the preagglomerate.

In those applications where a component of the preagglomerate mixture is prehydrated, it may be advantageous to mix the material with wetted, gypsum-containing solids or slurry produced in lime scrubbing stack gases to remove sulfur dioxide. Lime scrubber solids typically contain from about 15% to about 30% by weight water. The water present in the lime scrubber solids reacts with CaO and other calcium-containing compounds having the potential to be hydrated in the material to be prehydrated and the solids further dilute the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture. In addition to providing a convenient and economical source of prehydration water, including wetted lime scrubber solids in the preagglomerate mixture is advantageous in those applications where a sulfur-containing agglomerate is desired. Moreover, lime scrubber solids may provide a source of calcium, and gypsum in particular, having a lower concentration of heavy metals than particulate calcium sources obtained from other sources and thereby serve as a more effective buffer in reducing the concentration of heavy metals or other potentially harmful components in the agglomerate.

The composition of cement kiln dust, lime kiln dust, manure ash and other components of the particulate calcium source containing CaO and other calcium-containing compounds having the potential to be hydrated, as well as the preagglomerate mixture can vary substantially. One way of approximating the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in cement kiln dust and other materials in the preagglomerate mixture is to first dry the material to constant weight at about 100° C. to about 120° C. The dried material is then mixed with an amount of water in excess of the amount needed to totally hydrate the material (e.g., an equivalent weight of water) and dried again to constant weight at about 100° C. to about 120° C. The concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the material can then be approximated from the difference between the weight of water added and the weight of the material after the second drying. This differential represents the amount of water reacted with CaO and other calcium-containing compounds having the potential to be hydrated present in the material to form hydrates and can be used to approximate the concentration of such compounds in the material and ultimately the preagglomerate mixture.

Alternatively, in the absence of a compositional analysis, a series of agglomeration trials may be used to determine whether the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate mixture needs to be reduced, either by limiting the amount of the source of these compounds introduced into the preagglomerate or by prehydrating all or some of the particulate calcium source and, if prehydration is employed, the amount of water required to adequately prehydrate the material. In the case of cement kiln dust, it has been found that the amount of water necessary to achieve the proper extent of partial-hydration is usually between about 3% and about 16% by weight, and more typically between about 4% and about 8% by weight based on the starting weight of cement kiln dust.

If components of the preagglomerate mixture are prehydrated, it is preferred that substantially each particle of the material be uniformly coated with water to assure greater compositional uniformity in the prehydrated material. This may be achieved by using a high energy pin, auger, paddle or ribbon type mixer capable of intimately mixing the material and water. In order to enhance the degree of contact between the material to be prehydrated and the water and provide other beneficial effects, it is preferred to reduce the particle size of the material, if necessary, by ballmilling or other suitable means to achieve a particle size distribution as described below.

After the material to be prehydrated and water have been thoroughly mixed, the moistened material is preferably conditioned by storing it for a time sufficient so that substantially all of the water is reacted with the material. The moistened material discharged from the mixer may be stored in a conditioning bin wherein the hydration reaction between the water and the material is completed. In general, storage periods (i.e., conditioning times) from about 1 hour to as much as 24 hours are preferred. The hydration reaction which occurs upon combining cement kiln dust and similar materials with water is highly exothermic and its progress is easily monitored as the moistened material is conditioned by measuring the temperature rise as the material reacts with the water. After conditioning, the partially-hydrated material is substantially dry. Again, since the composition of cement kiln dust, lime kiln dust, manure ash and other components of the particulate calcium source may vary considerably, it may be desirable to conduct a series of trials with a particular material varying the storage time in order to ensure prehydration is accomplished as desired.

Preferably, the particulate calcium source used to prepare the agglomerate is finely divided. More specifically, it is preferred that particulate calcium source comprise a mixture of particles having a size distribution of which less than about 3% by weight, more preferably, less than about 1% by weight is +20 mesh and less than about 10% by weight is −20 +100 mesh. More preferably, less than about 20% by weight of the particles in the mixture is −100 +150 mesh. Even more preferably, less than about 25% by weight of the particulate calcium source is −100 +200 mesh. In accordance with even more preferred embodiments of the present invention, at least about 50% by weight of the particles in the mixture are −200 mesh. Still more preferably, at least about 75% by weight of the particles in the mixture are −200 mesh. In a still more preferred embodiment, at least about 75% by weight of the particles in the mixture are −200 mesh and at least about 5%, at least about 25%, or even at least about 50% by weight are −250 mesh. In accordance with a still further preferred embodiment, at least about 75% by weight of the particles in the mixture are −200 mesh and at least about 5%, at least about 25%, or even at least about 50% by weight are −325 mesh. In accordance with an especially preferred embodiment of the present invention, essentially all (e.g., at least about 90% by weight) of the particles of the particulate calcium source used to prepare the agglomerate are −100 mesh, preferably −150 mesh, more preferably −200 mesh, even more preferably −250 mesh, still more preferably −325 mesh and optimally −400 mesh. By utilizing a finely divided particulate calcium source in accordance with the preceding description, conversion of the calcium to plant-usable form (i.e., ionic calcium) once the agglomerate is incorporated into soil is expedited and optimum calcium saturation of the treated soil may be more readily attained. If necessary, ballmilling or other suitable means may be employed to obtain a desired particle size distribution in the particulate calcium source.

In order to provide agglomerates exhibiting a relatively uniform composition throughout and avoid segregation of the individual components in the agglomerates, it is preferred that all of the materials incorporated therein be similarly sized. However, the particles of the various additives which may be present in the agglomerates may be somewhat larger than the particles of the calcium source. Thus, for example, it is preferred that the mixture of all the various materials incorporated into the agglomerates have a particle size distribution of which less than about 1% by weight is +20 mesh and less than about 15% by weight is −20 +100 mesh. More preferably, not more than about 25% by weight of these particles is −100 +150 mesh. Still more preferably, at least about 20% by weight of the particles in the mixture are −200 mesh. In a still more preferred embodiment, at least about 50% by weight of the particles in the mixture are −200 mesh and at least about 5%, at least about 25%, or even at least about 50% are −325 mesh. As with the calcium source, it may be necessary to reduce the particle size of the primary nutrient source and other additives by ballmilling or other suitable means in order to obtain the desired particle size distribution.

The agglomerates of the present invention are prepared by pelletizing a preagglomerate mixture prepared by combining a water-soluble binder, the particulate calcium source (some or all of which may have been prehydrated) and, optionally, the other ingredients previously mentioned. The materials combined in the preagglomerate are present in proportions sufficient to provide an agglomerate of the desired composition. The preagglomerate may contain a portion of the water required for pelletizing.

The water-soluble binder may be combined with the other components of the preagglomerate either as a solid or as an aqueous solution of the binder. If an aqueous solution of a lignosulfonate salt is employed, the solution suitably contains from about 48% to about 60% by weight solids. If a solid binder is used, it is preferred that a portion of the water necessary for agglomeration of the preagglomerate (e.g., approximately two-thirds) be added along with the binder to promote thorough mixing of the binder with the other components of the preagglomerate. It is preferred that substantially each particle of the preagglomerate be coated with binder. This ensures uniformity in both the preagglomerate and in the final product and may be achieved by using a high energy pin, auger, paddle or ribbon type mixer capable of intimately mixing the components of the preagglomerate. Preferably, water and the binder are introduced at two or more locations into the mixer.

Although in the preceding description the prehydration of the particulate calcium source and addition of the binder were described as two distinct steps, it should be understood that prehydration of the calcium source and addition of the binder could take place simultaneously in a single step. For example, the binder may be added to the particulate calcium source as an aqueous solution of the binder, the binder solution containing sufficient water to achieve the appropriate degree of hydration of the calcium source. In such an operation, the calcium source and binder solution could be combined in a high energy mixture and then conditioned for a time sufficient to allow substantially all of the water to react with the calcium source. A portion of the water necessary for pelletizing could then be added to the conditioned material containing the binder along with any additives to form the preagglomerate. Similarly, the particulate calcium source, a solid water-soluble binder and an appropriate amount of water could be mixed intimately in a high energy mixture, conditioned and mixed with additional water and any additives to form a suitable preagglomerate.

The moistened preagglomerate mixture is fed directly to any suitable agglomeration device as is known in the art and pelletized to form the agglomerates. Once the agglomerates are formed, the binder and particulate calcium source form a matrix comprising the binder disposed within interstices between particles which binds the agglomerates together. Suitable pelletizing devices include drum, tub and shallow pan disc pelletizers or any other suitable tumble or growth agglomeration device. Preferably, a shallow-pan disc pelletizer is employed as the agglomeration device. Once the degree of tilt and rotational speed of the pan are determined, pelletizing of the moistened preagglomerate proceeds as is well known to those skilled in the art. In addition to these variables, more water is typically added in the pan to optimize the size and consistency of the agglomerates produced on the shallow pan disc pelletizer. The various parameters of the pelletizing step are controlled as is known in the art so as to produce agglomerates having a size suitable for broadcast or row placement using conventional fertilizer application equipment. Typically the agglomerates should be −3 +40 mesh, more preferably −6 +16 mesh.

After the agglomerates are discharged from the pelletizer, they are dried to remove a large portion of the internal water which is initially present in the newly-formed agglomerates. Active drying of the agglomerates is preferred to obtain a product having the desired mechanical strength and disintegration characteristics. If the agglomerates are not actively dried by heating, the water present in the freshly pelletized agglomerates may continue to react with the remaining components of the particulate calcium source which can still be hydrated and eventually form very hard, substantially non-disintegrable agglomerates resembling concrete. Preferably, the newly formed agglomerates are dried to reduce their moisture content to less than about 1% by weight, more preferably to less than about 0.5% by weight.

The agglomerates may be dried in any suitable apparatus. For example, drying may take place in an oven maintained at a temperature from about 100° C. to about 140° C. or a vibrating fluidized bed dryer or rotary dryer may be employed. In a continuous process, vibrating fluidized bed or rotary dryers are preferred since migration of the binder towards the exterior of the agglomerate is reduced, providing a more uniform product exhibiting improved mechanical strength. If a vibrating fluidized bed dryer is used, the dryer is suitably operated with a drying air entrance temperature of about 315° C. and an exit air temperature of about 95° C. However, these temperatures may vary significantly with the residence time of the agglomerates in the dryer. Preferably, the agglomerates do not exit the dryer at a temperature in excess of about 65° C. Depending upon the additives incorporated into the agglomerate, the drying temperatures noted above may have to be decreased in order to avoid melting the agglomerate. Furthermore, once drying is complete, it is preferred to allow the agglomerates to cool before piling in order to avoid the agglomerates from clumping together.

Dried agglomerates of the desired size may be separated using an air induction vibrating screen separator of the type available from Derrick Corporation, Buffalo, N.Y.

Once dried, the agglomerates should have sufficient mechanical strength to withstand normal handling, transportation and blending without fracturing and without excessive sloughing to form dust. There are several standardized methods that may be used for measuring mechanical strength of granular materials. However, a simple and widely-accepted standard is crush strength. Crush strength is measured by determining the minimum mass which crushes an agglomerate of particular size when the mass is placed on the agglomerate. In the practice of the present invention, the drying and removal of water from the newly-formed agglomerates is controlled such that dried agglomerates having a size ranging from −7 to +8 mesh exhibit an average green crush strength of at least about 2 pounds (about 0.9 kg), preferably at least about 4 pounds (about 1.8 kg), more preferably at least about 6 pounds (about 2.7 kg), still more preferably at least about 8 pounds (about 3.6 kg) and optimally at least about 9 pounds (about 4.1 kg). By green crush strength it is meant the crush strength of the dried agglomerates immediately after drying. In our experience, we have found that in some instances the newly dried agglomerates continue to increase in hardness as they age. This may be due to residual moisture present in the dried agglomerates which continues to react with and hydrate components of the agglomerate, resulting in further hardening of the agglomerate.

In order to inhibit dusting of the agglomerated product, a conventional dust control agent may be employed. For example, a dust control agent such as that sold by Arr-Maz Products, Winter Haven, Fla. 33880, under the product designation DUSTROL 30-52 may be spray applied to the heated agglomerates exiting the dryer.

Other additives may also be spray applied to the finished agglomerates. For example, if the agglomerate contains a source of nitrogen, it may be advantageous to apply a coating of a nitrogen volatilization inhibitor such as that commercially available from IMC Global, Bannockburn, Ill. 60015, under the trademark “AGRATAIN”.

Alternatively, such a nitrogen volatilization inhibitor could be incorporated into the preagglomerate mixture.

In certain states of the United States of America, liming agents such as the agglomerates of the present invention must comply with local ordinances which establish guidelines for the disintegration characteristics of such agents when exposed to water. Generally, liming agents should disintegrate once incorporated in the soil and exposed to water (e.g., rain) so that the various beneficial components of the agent can be utilized by the soil. In addition to substantial mechanical strength, the agglomerates made in accordance with the present invention disintegrate rapidly when immersed in water. Once exposed to water, the water-soluble binder in the agglomerates is readily dissolved, causing the agglomerates to disintegrate into particles of substantially the same size as the raw materials used to form the agglomerates, thereby allowing the agglomerates of the present invention to serve as an effective liming agent and deliver their nutrient values to the soil. In a preferred embodiment, the agglomerates of the present invention will dissolve in less than 10 minutes, more preferably in less than 5 minutes, still more preferably in less than 3 minutes, still more preferably in less than 2 minutes, and optimally in less than 1 minute when immersed in water at about 25° C.

A process flow diagram is presented in the figure illustrating an example of the type of equipment and flow scheme which may be used in practicing the present invention.

If prehydration of the particulate calcium source is employed, the calcium source is loaded into bin 1 and discharged by feeder 2 at a predetermined rate into a high energy mixer 3 along with water from pump 4 fed to the mixer at a rate sufficient to achieve the desired degree of hydration. Suitable high energy mixing devices include the device shown in U.S. Pat. No. 4,881,887 (Holley) sold by Ferro-Tech, Inc., Wyandotte, Mich. 48192 under the trademark “FERRO-TECH-TURBULATOR” and those available from Feeco Corporation, Greenbay, Wis. After sufficient residence time in mixer 3 to ensure intimate contact between the calcium source and the water, the hydrated mixture is discharged from mixer 3 into conditioning bin 5 and stored for a period of time sufficient to ensure that substantially all of the water has reacted with the particulate calcium source.

After conditioning, hydrated material is then discharged at a predetermined rate from bin 5 by feeder 6 into a second high energy mixer 7 along with a water-soluble binder, either in a liquid or a solid form, fed to mixer 7 at a predetermined rate from storage bin 8.

Alternatively, the water-soluble binder could be combined with the particulate calcium source in mixer 3.

If prehydration of the particulate calcium source is not employed, it should be understood that bin 1, feeder 2 high energy mixer 3 and pump 4 are omitted from the process shown in the figure and instead, the particulate calcium source is loaded into bin 5.

Additional water for pelletizing from pump 9 may be added to mixer 7 as needed to form the preagglomerate. If a product comprising the particulate calcium source and binder with no other additives is desired, then the preagglomerate issues from mixer 7 directly onto a suitable agitated agglomeration device 10 (e.g., a shallow pan disc pelletizer). Preferably, the preagglomerate is pelletized using a shallow pan disc pelletizer of the type shown in U.S. Pat. Nos. 4,726,755 (Holley) and 3,883,281 (Holley) sold by Ferro-Tech, Inc., Wyandotte, Mich. 48192 under the trademark “FERRO-TECH”.

If primary plant nutrient source (e.g., potash, urea and other N-P-K fertilizer components), other secondary plant nutrient source (e.g., limestone) and/or a micronutrient source additive are desired in the final agglomerates, these additives may be fed from bins 11 and 12 directly into mixer 7 along with the particulate calcium source from feeder 6, binder from storage bin 8 and additional water from pump 9 to form a suitable preagglomerate which is then fed to agglomeration device 10.

Agglomerates of the desired size discharged from the agglomeration device may then be fed directly into a suitable drying device (not shown) for drying.

It is known that N-P-K fertilizer ingredients have a generally acidifying effect on the soils into which they are incorporated which in turn has detrimental effects on beneficial microorganisms living in the soil. Furthermore, transfer of nutrient values from the soil to plants is generally hindered under acidic conditions. Thus, a problem encountered when introducing a primary plant nutrient source into soil is that the tendency of the fertilizer ingredient to lower the pH of the soil is counter productive to efficient utilization of the nutrient by beneficial microorganisms and plant life in the soil. As a result, nutrient values may be under utilized and eventually wasted as they are leached from the soil by precipitation and irrigation water. This is both costly and a significant contributor to pollution of adjacent ground and surface waters.

The agglomerates in accordance with the present invention may be employed in a method to introduce nutrient values into cultivated soil by applying to the soil an agglomerate comprising a particulate calcium source and a primary plant nutrient source and/or micronutrient source as previously described. The intimate mixture of a particulate calcium source and primary plant nutrient source within the agglomerate counteracts the acidifying effect of the N-P-K fertilizer component as the agglomerate breaks down in the soil thereby allowing more rapid transfer of nutrients to plant life and reducing nutrient loss and pollution due to leaching.

It has been observed that the beneficial effects of combining a particulate calcium source with a primary plant nutrient source in close proximity as in an agglomerate for application to the soil are further improved by observing certain criteria. First, the particulate calcium source preferably has a particle size distribution as previously described. The finely-divided calcium-containing particles in intimate mixture with the N-P-K fertilizer component more readily solubulized in the soil and rapidly counteracts acidifying effects so that the rate of nutrient transfer to the plants is enhanced. Generally, the finer the particle size distribution of the particulate calcium source the better. Secondly, the particulate calcium source should be selected so as to have a relatively high calcium carbonate equivalent (CCE) value. Preferably, the particulate calcium source has a calcium carbonate equivalent value in excess of 85%, more preferably in excess of about 90%, and most preferably in excess of about 92.5%. Furthermore, it is preferred that the particulate calcium source contain appreciable quantities of CaO and/or Ca(OH)₂ such that combined concentration of these compounds in the particulate calcium source is at least about 3% by weight, more preferably at least about 5% by weight. It is believed that CaO and Ca(OH)₂ exhibit exceptional acid neutralization capacity. Furthermore, these compounds are more readily converted to plant-usable ionic calcium than calcium carbonate (CaCO₃), gypsum (CaSO₄.2H₂O) and other calcium compounds typically present in soil liming agents and thereby more readily assist in the transport of nutrient values from the soil to plant life.

Although an important plant nutrient, excessive concentrations of magnesium in the soil is not conducive to the transfer of primary plant nutrients (e.g., phosphates) and micronutrients from the soil to plant life. Furthermore, the presence of magnesium in agglomerates containing a particulate calcium source combined with a primary plant nutrient source and/or micronutrient source is believed to hinder utilization of the nutrient values by plant life once the agglomerate disintegrates after being applied to the soil. Accordingly, the magnesium content of the agglomerates produced in accordance with the present invention is preferably no greater than about 2.5% by weight, more preferably, no greater than about 1.5% by weight and optimally no greater than about 1.0% by weight. Conventional soil liming agents often include significant quantities of magnesium compounds. Thus, special care should be taken to monitor the concentration of magnesium-containing compounds introduced into the preagglomerate along with the particulate calcium as well as other components of the preagglomerate so as to produce an agglomerate having the desired magnesium content.

The present invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or manner in which it may be practiced. In the proceeding examples, reference to weight percentages are based on the starting weight of cement kiln dust unless otherwise stated.

EXAMPLE 1

In this example, agglomerates were made from preagglomerate mixtures containing varying amounts of CaO combined with CaCO₃, urea and/or potash fines along with an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) as a binder. The preagglomerates were formed by thoroughly mixing CaO with measured quantities of CaCO₃, urea and/or potash fines. The CaO, CaCO₃ urea and potash fines each exhibited a particle size of −100 mesh. Once formed, the preagglomerate was then hand fed to a shallow pan disc pelletizer and formed into agglomerates. In some trials, the aqueous solution of lignosulfonate binder was mixed with the other components of the preagglomerate before being introduced onto the pan, while in other trials the binder was added to the other materials after they were introduced onto the pan. It is preferred that the binder be thoroughly incorporated into the preagglomerate mixture prior to being introduced into the pan. During pelletizing, approximately 5 to 8 weight percent of additional water (based on the weight of the preagglomerate including the lignosulfonate binder) was sprayed onto the agglomerates as they formed in the pan. The agglomerates were removed from the pan by hand and dried in an oven at 60-850° C. for approximately 30 minutes. After drying, the resulting agglomerates were screened to produce agglomerates having a size ranging from approximately −6 to +16 mesh. If possible, the green crush strength dried, screened agglomerates was determined. Set forth in Table 2 below is the composition of the preagglomorates and the observed results.

TABLE 2 Preagglomerate Composition (wt %) Results CaO Potash CaCO₃ Urea Binder Crush strength (lb) 95 — — — 5 fell apart 50 — 45 — 5 fell apart 25 — 70 — 5 fell apart 10 — 85 — 5 fell apart 7 — 88 — 5 4.3 5 — 90 — 5 6.4 3 — 92 — 5 9.0 5 — 88 — 7 7.0 7 — 86 — 7 4.2 10 — 81 — 9 −2 50 — — 45 5 fell apart 25 — — 70 5 fell apart 10 — — 85 5 3.0 7 — — 88 5 5.8 5 — — 90 5 8.2 3 — — 92 5 9.6 10 — — 83 7 6.0 7 — — 86 7 7.1 5 — — 88 7 8.1 50 45 — — 5 fell apart 25 70 — — 5 fell apart 10 85 — — 5 3.2 7 88 — — 5 5.9 5 90 — — 5 8.0 3 92 — — 5 9.2 10 83 — — 7 5.3 7 86 — — 7 6.9 5 88 — — 7 8.0 50 22.5 — 22.5 5 fell apart 25 35 — 35 5 fell apart 10 42.5 — 42.5 5 3.2 7 44 — 44 5 6.0 5 45 — 45 5 7.9 3 46 — 46 5 8.4

EXAMPLE 2

Three samples of cement kiln dust taken directly from the dust collection apparatus of a portland cement plant (Plant A) were hydrated using varying amounts of water. The three samples were combined in a high energy mixer with 10, 14 and 16 weight percent water, respectively and stored in sealed containers for approximately 24 hours. Each sample of hydrated material was then mixed with 7 weight percent potash, 5 weight percent of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) and additional water in a high energy mixer to form a preagglomerate. The preagglomerate was then fed to a FERRO-TECH brand shallow pan disc pelletizer and formed into agglomerates. During pelletizing, approximately 5 weight percent of additional water was added to the forming agglomerates. The agglomerates had a size ranging from approximately −6 to +16 mesh. These agglomerates were then oven dried at 120° C. for approximately 24 hours. The dried agglomerates from all three runs exhibited a green crush strength of approximately 3 pounds (about 1.4 kg) and disintegrated in a matter of minutes when immersed in water.

EXAMPLE 3

Four samples of cement kiln dust were taken directly from the dust collection apparatus of each of two other portland cement plants (Plants C and L) and hydrated using varying amounts of water. The four samples from each plant were combined in a high energy mixture with 4, 30 6, 8 and 10 weight percent water, respectively, and stored in sealed containers for approximately 24 hours. Each of the samples of hydrated material was then mixed with a weight percent of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) and additional water in a high energy mixer to produce a preagglomerate. The preagglomerate was then fed to a FERRO-TECH brand shallow pan disc pelletizer and formed into agglomerates. During pelletizing, approximately 2.5 to 5 weight percent of additional water was added to the forming agglomerates.

The agglomerates had a size ranging from approximately −6 to +16 mesh. These agglomerates were then oven dried at 120° C. for approximately 24 hours. The dried agglomerates from all eight runs exhibited a green crush strength of approximately 1 to 3 pounds (about 0.5 to 1.4 kg). The crush strength was found to increase as the amount of water used to partially hydrate the dust was increased. However, the agglomerates made from the dust hydrated with 4 weight percent water disintegrated in 1 to 2 minutes when immersed in water, while the agglomerates made from the dust hydrated with 10 weight percent water disintegrated in 10 to 20 minutes. The disintegration rate of agglomerates made from the dust samples hydrated with 6 and 8 weight percent water fell between these two values.

EXAMPLE 4

Four samples of cement kiln dust taken directly from the dust collection apparatus of Plant C were processed exactly as described in Example 3 except that (1) in addition to the aqueous solution of NORLIG A brand calcium lignosulfonate, 8 weight percent of potash was added to the hydrated material; and (2) instead of approximately 2.5 to 5 weight percent, approximately 10 weight percent of additional water was added to the forming agglomerates during pelletizing. Similar results to those in Example 3 were achieved. The dried agglomerates from all four runs exhibited a green crush strength of approximately 1 to 3 pounds (about 0.5 to 1.4 kg) which tended to increase as the amount of water used to partially hydrate the dust was increased. Similarly the disintegration rate of the agglomerates decreased as the amount of water used to partially hydrate the dust was increased.

The data from Example 3 and the present example demonstrate the effect of varying the amount of water used to hydrate the dust on the rate of disintegration of the final agglomerate. Thus, by varying the amount of water used to hydrate a particular dust, the disintegration characteristics of the agglomerate may be altered as desired. Thus, in Example 3 and the present example, if a high rate of disintegration is desired, then the agglomerates made using 4 weight percent water would be preferred.

The agglomerates made in the present example were subjected to a wet sieving test to better examine the disintegration characteristics of these pellets. The wet sieving test was conducted by stacking five sieves of differing mesh size such that the sieve opening decreased progressively. from the top sieve to the bottom sieve. After weighing, a sample of the agglomerates made in the present example was immersed in water for approximately 48 hours. The moistened material was then deposited on the top sieve and subjected to a gentle spray of wash water. As the material disintegrated, it passed through the top sieve along with the wash water and was deposited, onto the next sieve. Wash water was applied to the top sieve until the water draining through the sieve was substantially clear. The top sieve was then removed and the washing process repeated on each subsequent sieve in the stack in the same fashion as described above. Each of the sieves and any material remaining on the screens were heated to remove substantially all the moisture and then weighed. The weight of material (dry) which did not pass through each sieve was determined by subtracting the tare weight of each sieve. Summarized in Table 3 below is the weight percentage of material (based on the starting weight of the sample of agglomerates) which did not pass through each of the five sieves in the wet screening test.

TABLE 3 Tyler Standard Weight % Sieve Sieve Series Not Passing Top 9 0 Second 20 0 Third 32 0 Fourth 60 0.8 Bottom 100 7.0

As noted in Table 3, the agglomerates subjected to the wet screening test disintegrated such that all of the resulting particulate matter had a nominal diameter less. than 500 μm (i.e., −32 mesh) and substantially all of the resulting particles had a nominal diameter less than 150 μm (i.e., −100 mesh).

EXAMPLE 5

A sample of cement kiln dust taken directly from the dust collection apparatus of Plant A was processed exactly as described in Example 2 using 10 weight percent water to hydrate the dust and using only potash (7 weight percent) as the binder. After oven drying, the resulting agglomerates having a size ranging from approximately −6 to +16 mesh exhibited a green crush strength of approximately 3 pounds (about 1.4 kg) and disintegrated in a matter of minutes when immersed in water.

EXAMPLE 6

A sample of cement kiln dust taken directly from the dust collection apparatus of Plant A was processed exactly as described in Example 2 using 14 weight percent water to hydrate the dust and using only 7 weight percent of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) as the binder. A slightly larger amount of the lignosulfonate salt solution was used than in Example 2 to compensate for the loss of binding action due to the absence of potash. After oven drying, the resulting agglomerates having a size ranging from approximately −6 to +16 mesh exhibited a green crush strength ranging from approximately 2 to 3 pounds (about 1 to 1.4 kg) and disintegrated in a matter of minutes when immersed in water.

EXAMPLE 7

A sample of cement kiln dust taken directly from the dust collection apparatus of Plant A was processed exactly as described in Example 2 except that the dust was not hydrated before adding the binder. After oven drying, the resulting agglomerates having a size ranging from approximately −6 to +16 mesh exhibited essentially no crush strength, falling apart by simple vibration or touch of the hand.

This example demonstrates the importance of controlling the concentration of CaO and other calcium-containing compounds having the potential to be hydrated in the preagglomerate. Unless the cement kiln dust is sufficiently hydrated before pelletizing or combined with materials in the preagglomerate to sufficiently dilute the hydration potential, the components of the preagglomerate will tend to hydrate excessively during formation of the agglomerate. Such hydration is accompanied by a volumetric expansion of the formed agglomerate which renders the agglomerate weak and undesirable for agricultural uses.

EXAMPLE 8

A sample of cement kiln dust taken directly from the dust collection apparatus of Plant C was combined in a high energy mixture with 14 weight percent water using a residence time of approximately 1 hour. The hydrated material was then mixed with both 7 weight percent potash and 5 weight percent of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) in a high energy mixer to form a preagglomerate. The preagglomerate was then led to a FERRO-TECH brand shallow pan disc pelletizer to form agglomerates. During pelletizing, approximately 2.5 weight percent of additional water was added to the forming agglomerates. The agglomerates formed had a size ranging from approximately −6 to +16 mesh. These agglomerates were then oven dried at 120° C. for approximately 24 hours. The dried agglomerates exhibited a green crush strength of from approximately 1 to 2 pounds (about 0.5 to 0.9 kg) and disintegrated in 10 to minutes when immersed in water.

It is believed that the somewhat lower crush strength of the agglomerates produced in this example as compared to Example 2 is a result of the cement kiln dust containing lower concentrations of CaO and other components which hydrate upon exposure to water as compared to the dust used in Example 2. Therefore, the amount of hydration water should be reduced.

EXAMPLE 9

A sample of cement kiln dust from Plant C was removed from an outdoor disposal site where it had been exposed to atmospheric moisture and rain and was presumably completely hydrated. This sample was formed into agglomerates without further hydration and without using a binder. During pelletizing, approximately 5 weight percent of additional water was added to the forming agglomerates. The agglomerates formed had a size ranging from approximately −6 to +16 mesh. These agglomerates were then oven dried at 120° C. for approximately 24 hours. The dried agglomerates exhibited a green crush strength of approximately 6 pounds (about 25 2.7 kg) but did not disintegrate after several months of immersion in water and, thus, would not be suitable for agricultural uses.

This example demonstrates the importance of adding a water-soluble binder in producing an agglomerate having desirable disintegration characteristics.

EXAMPLE 10

A 2.3 kg sample of cement kiln dust taken directly from the dust collection apparatus of Plant C was ballmilled to a bulk density of about 863 kg/m³. The ballmilled dust was hydrated by combining it with 8 weight percent (0.18 kg) water in a high energy mixer. After two minutes of mixing, the material was removed from the mixer and transferred into a sealed container. In order to simulate bin storage of a large quantity of hydrating cement kiln dust, the sealed container was placed in an oven maintained at about 65° C. for a period of about 24 hours. Approximately 1 kg of the hydrated dust was then mixed with about 1 kg of ballmilled urea and approximately 0.16 kg of an aqueous solution of Is NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) in a high energy mixer for approximately 18 seconds. This mixture was then fed to a FERRO-TECH brand shallow pan disc pelletizer and formed into agglomerates. Approximately 7.5 weight percent of water (based on combined weight of hydrated dust and urea) was added to the mixture in the form of solvent in the aqueous binder solution and as pelletizing water in the pan. The formed agglomerates were removed from the pan, allowed to stand at room temperature for about 24 hours and dried in a portable fluidized bed dryer at 38° to 50° C. for approximately 15 minutes. The dried agglomerates were sieved screened to a size ranging from −6 to +16 mesh. Agglomerates ranging in size from −7 to +8 mesh exhibited a green crush strength of about 8 pounds (about 3.6 kg) and a bulk density of about 855 kg/m³.

The dried agglomerates were analyzed for both total calcium and total nitrogen content using comprehensive analysis methods. Total calcium content was determined by digesting a sample of pulverized agglomerates in HCl over heat, diluting the resulting solution and subjecting it to atomic absorption analysis. Total nitrogen content was determined in accordance with Association of Official Analytical Chemist (AOAC) Method No. 2.059. The agglomerates contained 14.85 weight percent calcium and 19.40 weight percent nitrogen. For purposes of comparative liming capacity, the Ca content of the agglomerates in this example corresponds to 20.78 weight percent as CaO and 37.11 weight percent as CaCO₃.

EXAMPLE 11

A 2.3 kg sample of cement kiln dust taken directly from the dust collection apparatus of Plant L was ballmilled to a bulk density of about 679 kg/m³. The ballmilled dust was hydrated by combining it with 8 weight percent (0.18 kg) water in a high energy mixer. After two minutes of mixing, the material was removed from the mixer and transferred into a sealed container. In order to simulate bin storage of a large quantity of hydrating cement kiln dust, the sealed container was placed in an oven maintained at about 65° C. for a period of about 24 hours. Approximately 1 kg of the hydrated dust was then mixed with about 1 kg of ballmilled urea and approximately 0.16 kg of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) in a high energy mixer for approximately 18 seconds. This mixture was then fed to a FERRO-TECH brand shallow pan disc pelletizer and formed into agglomerates. Approximately 9.5 weight percent of water (based on combined weight of hydrated dust and urea) was added to the mixture in the form of solvent in the aqueous binder solution and as pelletizing water in the pan. The formed agglomerates were removed from the pan, allowed to stand at room temperature for about 24 hours and dried in a portable fluidized bed dryer at 38° to 50° C. for approximately 15 minutes. The dried agglomerates were sieved screened to a size ranging from −6 to +16 mesh. Agglomerates ranging in size from −7 to +8 mesh exhibited a green crush strength of about 8 pounds (about 3.6 kg) and a bulk density of about 714 kg/m³.

The dried agglomerates were analyzed for both total calcium and total nitrogen content using the same methods as described in Example 10. The agglomerates contained 14.19 weight percent calcium and 19.50 weight percent nitrogen. For purposes of comparative liming capacity, the Ca content of the agglomerates in this example corresponds to 19.86 weight percent as CaO and 35.47 weight percent as CaCO₃.

EXAMPLE 12

A 2.3 kg sample of cement kiln dust taken directly from the dust collection apparatus of Plant C was ballmilled to a bulk density of about 863 kg/³ The ballmilled dust was hydrated by combining it with 8 weight percent (0.18 kg) water in a high energy mixer. After two minutes of mixing, the material was removed from the mixer and transferred into a sealed container. In order to simulate bin storage of a large quantity of hydrating cement kiln dust, the sealed container was placed in an oven maintained at about 65° C. for a period of about 24 hours. Approximately 1.5 kg of the hydrated dust was then mixed with about 0.5 kg of particulate dolomitic limestone, approximately 0.16 kg of an aqueous solution of NORLIG A brand calcium lignosulfonate (about 54 weight percent lignosulfonate salt) and 75 ml of water in a high energy mixer for approximately 18 seconds. This mixture was then fed to a FERRO-TECH brand shallow pan disc pelletizer and formed into agglomerates. Approximately 18 weight percent of water (based on combined weight of hydrated dust and dolomitic limestone) was added to the mixture in the form of solvent in the aqueous binder solution and as pelletizing water in the pan. After being removed from the pan, a sample of the agglomerates were dried immediately in a portable fluidized bed dryer at 380 to 50° C. for approximately 15 minutes, while the remainder of the agglomerates were allowed to first stand at room temperature for about 24 hours and then dried in the portable fluidized bed dryer. The dried agglomerates were sieved screened to a size ranging from −6 to +16 mesh. The agglomerates which were allowed to-stand 24 hours and having a size ranging from −7 to +8 mesh exhibited a green crush strength of about 2.4 pounds (about 1.1 kg) and a bulk density of about 1057 kg/M3, while similarly sized agglomerates which were dried immediately in the fluidized bed dryer exhibited green crush strengths between about 2 and about 3 pounds (between about 1 and about 1.4 kg). If desired, the green crush strength of the agglomerates could be increased by using a larger quantity of binder.

EXAMPLE 13

Urea (2.4 pounds), crushed limestone (0.8 pounds), and non-prehydrated cement kiln dust (0.8 pounds) were mixed with water (Test 13-1) or a binder (a solution of lignosulfonate having approximately 50% solids —Test 13-2) in a Model 12TB34 Batch Turbulator for 18 seconds to form preagglomerates. The preagglomerates were hand fed to a Model 024″ 2′0″ Disc Pelletizer in which water was being sprayed onto the disc at a 4:30/6:30 positions. The agglomerates were removed by hand and dried at 120° F. to produce screened dry pellets (−6 +16 mesh). The moisture content and bulk density of the starting materials are presented below in Table 4:

TABLE 4 Raw Data Moisture Bulk Density Urea N/A 636 kg/m₃ Limestone 0% 1330 kg/m₃ Cement Kiln Dust 0% 867 kg/m₃

The resulting agglomerates were analyzed and found to have the following characteristics:

TEST 13-1 Binder (water only) Amount of water at Batch Turbulator 50 ml Moisture from disc. 7% Product bulk density 764 kg/m³ Crush strength average (−6 +8 mesh) 6 pounds (2.7 kg) TEST 13-2 Binder 3% Lignin Amount of Water at Batch Turbulator 50 ml Moisture from Disc. 7% Product Bulk Density 772 kg/m³ Crush Strength Average (−6 +8 mesh) 7 pounds (3.2 kg)

EXAMPLE 14

The procedure of Example 13 was repeated except that urea (2.4 pounds) and cement kiln dust (1.6 pounds) were mixed with 50 ml water in the Batch Turbulator for 18 seconds. The results were as follows:

Moisture from Disc 7% Product Bulk Density 706 kg/m³ Crush Strength Average (−6 +8 mesh) 3 pounds (1.4 kg)

EXAMPLE 15

In this example, agglomerates were made from preagglomerate mixtures containing varying amounts of lime kiln dust, manure ash and potash fines along with KGA-300 liquid wood waste derivative as a binder. The lime kiln dust and manure ash were analyzed and determined to contain about 55% and about 7% by weight CaO, respectively. The lime kiln dust and manure ash exhibited a particle size distribution such that 90% of the particles were −300 mesh. The potash fines exhibited a particle size distribution such that 90% of the particles were −150 mesh.

The preagglomerate mixtures were formed by thoroughly mixing measured quantities of lime kiln dust, manure ash and potash fines with the liquid binder. The preagglomerate was hand fed to a shallow pan disc pelletizer and formed into agglomerates. In some trials, the liquid wood waste binder was mixed with the other components of the preagglomerate before being introduced onto the pan, while in other trials the binder was sprayed onto the other materials after they were introduced onto the pan. In order to render the liquid binder better suited for spray application, the binder was heated to about 80° C. It is preferred that the binder be thoroughly incorporated into the preagglomerate mixture prior to being introduced into the pan. During pelletizing, approximately 5 to 8 weight percent of additional water (based on the weight of the preagglomerate including the liquid binder) was sprayed onto the agglomerates as they formed in the pan. The agglomerates were removed from the pan by hand and dried in an oven at 60-85° C. for approximately 30 minutes. After drying, the resulting agglomerates were screened to produce agglomerates having a size ranging from approximately −6 to +16 mesh. If possible, the green crush strength of the dried, screened agglomerates was determined. Set forth in Table 5 below is the composition of the preagglomerates and the observed results.

TABLE 5 Preagglomerate Composition (wt %) Lime Kiln Manure Results Dust Ash Potash Binder Crush Strength (lb) 55 — 45 5 fell apart 25 — 70 5 fell apart 10 — 87 3 4.0 10 43.5 43.5 3 5.5 — 95 — 5 5.0

EXAMPLE 16

In this example, agglomerates were made from preagglomerate mixtures containing varying amounts of a mixture of lime kiln dust and wetted gypsum combined with potash fines along with KGA−300 liquid wood waste derivative as a binder. The lime kiln dust was analyzed and determined to contain about 55% by weight CaO. The lime kiln dust exhibited a particle size distribution such that 90% of the particles were −300 mesh. The potash fines exhibited a particle size distribution such that 90% of the particles were −150 mesh. The wetted gypsum was obtained from a lime scrubbing unit used to remove sulfur dioxide from the gaseous effluent of an electric power plant and was about 98% pure with a water content of about 22% by weight.

The lime kiln dust and wetted gypsum were combined in a weight proportion of 2 to 3 and mixed thoroughly. The resulting mixture was then allowed to set for approximately 12 hours, allowing water present in the wetted gypsum to react with the lime kiln dust. After conditioning in this fashion, the lime kiln dust/gypsum mixture appeared essentially dry to the touch. The preagglomerate mixtures were formed by thoroughly mixing measured quantities of the conditioned lime kiln dust/gypsum mixture, potash fines and the liquid binder. The preagglomerate was hand fed to a shallow pan disc pelletizer and formed into agglomerates. In order to render the liquid binder better suited for spray application, the binder was heated to about 80° C. During pelletizing, approximately 5 to 8 weight percent of additional water (based on the weight of the preagglomerate including the liquid binder) was sprayed onto the agglomerates as they formed in the pan. The agglomerates were removed from the pan by hand and dried in an oven at 60-85° C. for approximately 30 minutes. After drying, the resulting agglomerates were screened to produce agglomerates having a size ranging from approximately −6 to +16 mesh. If possible, the green crush strength of the dried, screened agglomerates was determined. Set forth in Table 6 below is the composition of the preagglomerates and the observed results.

TABLE 6 Preagglomerate Composition (wt %) Lime Kiln Dust/ Results Wetted Gypsum Potash Binder Crush Strength (lb) 50 45 5 3.5 30 65 5 6.0

In view of the above, it will be seen that the several objects of the invention are achieved.

As various changes could be made in the above-described invention without departing from the scope of the invention, it is indeed intended that all matter contained in the above description be interpreted as illustrative and not in a limiting sense. 

What is claimed is:
 1. A process for forming an agglomerate for use as a soil conditioning agent, the process comprising: preparing a preagglomerate containing a water-soluble binder and a particulate calcium source selected from the group consisting of limestone, dolomitic limestone, gypsum, hydrated lime and mixtures thereof, the particulate calcium source having a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series; and pelletizing the preagglomerate to form the agglomerate, the proportion of the particulate calcium source in the preagglomerate being sufficient such that the agglomerate comprises at least about 15% by weight of the particulate calcium source.
 2. A process as set forth in claim 1 wherein the particulate calcium source is selected from the group consisting of limestone, dolomitic limestone, gypsum and mixtures thereof and the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −325 mesh Tyler Standard Sieve Series.
 3. A process as set forth in claim 2 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −400 mesh Tyler Standard Sieve Series.
 4. An agglomerate for use as a soil conditioner, the agglomerate being formed by pelletizing a preagglomerate containing a water-soluble binder and particulate calcium source selected from the group consisting of limestone, dolomitic limestone, gypsum, hydrated lime and mixtures thereof, the particulate calcium source having a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series, the agglomerate having a size ranging from −7 to +8 Tyler Standard Sieve Series exhibiting an average green crush strength of at least about 2 pounds and comprising at least about 15% by weight of the particulate calcium source.
 5. An agglomerate as set forth in claim 4 wherein the particulate calcium source is selected from the group consisting of limestone, dolomitic limestone, gypsum and mixtures thereof and the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −325 mesh Tyler Standard Sieve Series.
 6. An agglomerate as set forth in claim 5 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −400 mesh Tyler Standard Sieve Series.
 7. A process for forming an agglomerate for use as a soil conditioning agent, the process comprising: preparing a preagglomerate containing a particulate calcium source, a primary plant nutrient source and a water-soluble binder, the particulate calcium source having a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series, the preagglomerate having a particle size distribution such that less than about 1% by weight of the preagglomerate is +20 mesh, less than about 15% by weight of the preagglomerate is −20 +100 mesh and not more than about 25% by weight of the preagglomerate is −100 +150 mesh Tyler Standard Sieve Series; and pelletizing the preagglomerate to form the agglomerate, the proportion of the particulate calcium source in the preagglomerate being sufficient such that the agglomerate comprises at least about 15% by weight of the particulate calcium source.
 8. A process as set forth in claim 7 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −325 mesh Tyler Standard Sieve Series.
 9. A process as set forth in claim 7 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −400 mesh Tyler Standard Sieve Series.
 10. A process as set forth in claim 7 wherein the particulate calcium source is selected from the group consisting of limestone, dolomitic limestone, gypsum, hydrated lime and mixtures thereof.
 11. A process as set forth in claim 10 wherein the particulate calcium source exhibits a calcium carbonate equivalent value in excess of about 85%.
 12. A process as set forth in claim 10 wherein the combined concentration of CaO and Ca(OH)₂ in the particulate calcium source is at least about 3% by weight.
 13. A process as set forth in claim 7 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −200 mesh and at least about 5% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 14. A process as set forth in claim 13 wherein the preagglomerate has a particle size distribution such that at least about 25% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 15. A process as set forth in claim 13 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 16. A process as set forth in claim 7 wherein the proportions of the particulate calcium source and the primary plant nutrient source in the preagglomerate are sufficient such that the agglomerate comprises about 15% to about 60% by weight of the particulate calcium source and about 10% to about 80% by weight of the primary plant nutrient source.
 17. A process as set forth in claim 16 wherein the primary plant nutrient source is selected from the group consisting of ammonium nitrate, ammonium sulfate, alkali metal nitrates, urea, rock phosphate, ammonium phosphate, bone meal slag, aluminum phosphate, superphosphate, potash, potassium salts and mixtures thereof.
 18. A process as set forth in claim 16 wherein the concentration of magnesium-containing compounds in the preagglomerate is such that the magnesium content of the agglomerate is no greater than about 2.5% by weight.
 19. A process as set forth in claim 18 wherein the concentration of magnesium-containing compounds in the preagglomerate is such that the magnesium content of the agglomerate is no greater than about 1.5% by weight.
 20. An agglomerate for use as a soil conditioner and provide a source of nutrient values, the agglomerate being formed by pelletizing a preagglomerate containing a particulate calcium source, a primary plant nutrient source and a water-soluble binder, the proportions of the particulate calcium source and the primary plant nutrient source in the preagglomerate being sufficient such that the agglomerate comprises about 15% to about 60% by weight of the particulate calcium source and about 10% to about 80% by weight of the primary plant nutrient source, the particulate calcium source having a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and at least about 90% by weight of the particulate calcium source is −200 mesh Tyler Standard Sieve Series, the preagglomerate having a particle size distribution such that less than about 1% by weight of the preagglomerate is +20 mesh, less than about 15% by weight of the preagglomerate is −20 +100 mesh and not more than about 25% by weight of the preagglomerate is −100 +150 mesh Tyler Standard Sieve Series, the agglomerate having a size ranging from −7 to +8 Tyler Standard Sieve Series exhibiting an average green crush strength of at least about 2 pounds.
 21. An agglomerate as set forth in claim 20 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series.
 22. An agglomerate as set forth in claim 20 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −325 mesh Tyler Standard Sieve Series.
 23. An agglomerate as set forth in claim 20 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −400 mesh Tyler Standard Sieve Series.
 24. An agglomerate as set forth in claim 20 wherein the particulate calcium source is selected from the group consisting of limestone, dolomitic limestone, gypsum, hydrated lime, and mixtures thereof.
 25. An agglomerate as set forth in claim 24 wherein the particulate calcium source exhibits a calcium carbonate equivalent value in excess of about 85%.
 26. An agglomerate as set forth in claim 24 wherein the combined concentration of CaO and Ca(OH)₂ in the particulate calcium source is at least about 3% by weight.
 27. An agglomerate as set forth in claim 20 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −200 mesh and at least about 5% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 28. An agglomerate as set forth in claim 27 wherein the preagglomerate has a particle size distribution such that at least about 25% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 29. An agglomerate as set forth in claim 27 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 30. An agglomerate as set forth in claim 20 wherein the primary plant nutrient source is selected from the group consisting of ammonium nitrate, ammonium sulfate, alkali metal nitrates, urea, rock phosphate, ammonium phosphate, bone meal slag, aluminum phosphate, superphosphate, potash, potassium salts and mixtures thereof.
 31. An agglomerate as set forth in claim 30 further comprising a micronutrient source, the micronutrient source comprising a source of at least one element selected from the group consisting of iron, copper, boron, selenium, chromium, vanadium, manganese, zinc and molybdenum.
 32. An agglomerate as set forth in claim 31 wherein the magnesium content of the agglomerate is no greater than about 2.5% by weight.
 33. An agglomerate as set forth in claim 32 wherein the magnesium content of the agglomerate is no greater than about 1.5% by weight.
 34. A method for introducing nutrient values into cultivated soil so as to inhibit leaching of the nutrient values from the soil and improve utilization of the nutrient values by plants grown in the soil, the method comprising applying to the soil an agglomerate formed by pelletizing a preagglomerate containing a particulate calcium source, a primary plant nutrient source and a water-soluble binder, the agglomerate comprising about 15% to about 60% by weight of the particulate calcium source, about 30% to about 80% by weight of the primary plant nutrient source and the water-soluble binder, the particulate calcium source exhibiting a calcium carbonate equivalent value in excess of about 85% and having a particle size distribution such that less than about 1% by weight of the particulate calcium source is +20 mesh, less than about 10% by weight of the particulate calcium source is −20 +100 mesh and at least about 90% by weight of the particulate calcium source is −200 mesh Tyler Standard Sieve Series, the preagglomerate having a particle size distribution such that less than about 1% by weight of the preagglomerate is +20 mesh, less than about 15% by weight of the preagglomerate is −20 +100 mesh and not more than about 25% by weight of the preagglomerate is −100 +150 mesh Tyler Standard Sieve Series, the agglomerate readily dissolving upon exposure to water to disintegrate into particles of the particulate calcium source and primary plant nutrient source.
 35. A method as set forth in claim 34 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −250 mesh Tyler Standard Sieve Series.
 36. A method as set forth in claim 34 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −325 mesh Tyler Standard Sieve Series.
 37. A method as set forth in claim 34 wherein the particulate calcium source has a particle size distribution such that at least about 90% by weight of the particulate calcium source is −400 mesh Tyler Standard Sieve Series.
 38. A method as set forth in claim 34 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −200 mesh and at least about 5% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 39. A method as set forth in claim 38 wherein the preagglomerate has a particle size distribution such that at least about 25% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 40. A method as set forth in claim 38 wherein the preagglomerate has a particle size distribution such that at least about 50% by weight of the preagglomerate is −325 mesh Tyler Standard Sieve Series.
 41. A method as set forth in claim 34 wherein the agglomerate further comprises a micronutrient source, the micronutrient source comprising a source of at least one element selected from the group consisting of iron, copper, boron, selenium, chromium, vanadium, manganese, zinc and molybdenum.
 42. A method as set forth in claim 34 wherein the magnesium content of the agglomerate is no greater than about 2.5% by weight.
 43. A method as set forth in claim 42 wherein the magnesium content of the agglomerate is no greater than about 1.5% by weight. 